Process for the production of a matted photographic material



United States Patent 3,507,678 PROCESS FOR THE PRODUCTION OF A MATTEDPHOTOGRAPHIC MATERIAL Ikuo Shimizu, Hideo Kawano, and Shunzo Yagami,Ashigara-Kamigun, Kanagawa, Japan, assignors to Fuji Shashin FilmKabushiki Kaisha, Ashigara-Kamigun, Kanagawa, Japan, a corporation ofJapan No Drawing. Filed Sept. 27, 1966, Ser. No. 582,268 Claimspriority, application Japan, Sept. 28, 1965, 40/ 59,267 Int. Cl. C03c.7/00, 1/74, 3/26; G03c N00 US. Cl. 117-34 4 Claims ABSTRACT OF THEDISCLOSURE Process for producing a photographic light sensitive materialhaving a matted surface, particularly developing the matted surface byapplying non-deliquescent crystalline water soluble salts to theprotective coating surface in fine sized particles.

The present invention relates to a process for producing a photographiclight-sensitive material having a matted surface.

In photographic light-sensitive material using silver halide, thesurface is matted, sometimes by applying to or in its light-sensitivelayer, protective layer or antihalation layer fine particles of starch,starch derivatives, synthetic resins such as polystyrene resin, orinorganic compounds, such as silicon dioxide, titanium dioxide, bariumsulfate and strontium sulfate, each being called a matting agent.

The first object of matting the surface of a photographiclight-sensitive material, in general, is to prevent adhesion of thelight-sensitive layers among themselves or with the antihalation layerat high temperature and high humidity. The second object is to preventthe unevenness of exposure caused by the Newton ring-like unevenness dueto tight adhesion of the layer and glass during printing when thephotographic light-sensitive material is for a negative material. Thethird object to make it easy to write on the surface of alight-sensitive material with a pencil or the like after copying whenthe lightseusitive material is a film for copying. The fourth object isto prevent the occurrence of obstacles by static electricity duringproduction or handling. Furthermore, the fifth object is to lower thecoefficient of friction, although it seems inconsistent.

However, such a matting agent cannot be adapted to all photographicmaterials unconditionally, except the case where it is employed for thepurpose of devitrifying as in a film for a second original, since thematting agent is white and opaque fine particles or difi'ers remarkablyin the index of refraction from a gelatin in which a sensitive silverhalide is suspended and hence it tends to damage the transparency of thefinished film. The use of a great amount should be avoided particularlyin the case where a very high transparency is required, for example, infilms for plate making and X-ray films.

Further, a method has also been proposed in which other matting agentsthan the above-mentioned, which can mat sufficiently the surface of alight-sensitive element and gives no bad influences on the transparencyof the support after photographic processings of developing,

3,507,678 Patented Apr. 21, 1970 fixing, water-Washing and the like, forexample, fine particles of a material capable of being dissolved off inan acid or alkaline solution, such as, zinc carbonate or strontiumcarbonate is added in a neutral or substantially neutral coatingsolution. However, such compound is often retained undissolved dependingupon the kind of a treating solution, the degree of fatigue, treatingtemperature, treating'time, etc., resulting in a bad influence upon thetransparency of a film after processings.

Accordingly, the object of the present invention is to overcome suchdisadvantages by matting the surface of a silver halide photographicmaterial with readily soluble fine particles not dependent upon the kindof treating solution, degree of fatigue, treating temperature, treatingtime, etc.

I In accordance with the present invention, there is provided a processfor the production of a photographic light-sensitive material having amatted surface, which is characterized by adding a water-soluble,non-deliquescent crystalline compound to a coating solution composed ofwater as a main solvent and gelatin as a binder in a proportion of l30%by weight to the gelatin, applying the resulting solution to the surfaceof a support or photographic material, coagulating the coating at a lowtemperature and drying whereby to deposit the fine crystals of saidcompound on the surface of the coating.

Illustrative of the water soluble, non-deliquescent crystallinecompounds used in the present invention are potassium sulfate, sodiumsulfate, zinc sulfate and cadmium sulfate.

The coating solution used in the present invention is a photographiclight-sensitive emulsion, coating solution for protecting and coatingsolution for antihalation, but another coating solution may be speciallyprepared. The coating solution of the present invention uses gelatin asa binder, but a water-soluble high molecular compound such aspolyvinyl-pyrrolidone, polyvinyl alcohol and hydroxyalkyl starch may beemployed together with gelatin.

The support is a plastic film, such as cellulose triacetate andpolyethylene terephthalate, having a subbing layer for advantaging thesubsequent coating and those on which a light-sensitive emulsion layeror antihalation layer is coated.

The solidification of the coating solution in the invention is carriedout by cooling it to a temperature of below the coagulation pointthereof, for example, by contacting the back side of the coating layerwith a cooled roller or exposing to a cooled air, preferably, at below10 C.

The drying of the coating in the invention is carried out by passing itthrough a stream of the air heated or at normal temperature and the airis preferably adjusted to a dry bulb temperature of 18-50" C. and arelative humidity of 25 The quantity of the compound used in ourinvention may vary with the degree of matting required, kind of acoating solution and drying conditions, but it is generally within 1-30%weight to the gelatin composing a layer. For example, a quantity of23-15% is preferably applied to the gelatin by weight in order toprevent adhesion in the case of an antihalation layer and 10-25% ispreferred in the case of applying to a protective layer in order toprevent electrification. The average size of fine particles deposited onthe surface is within a range of 1-10 microns, a slow drying resultingin relatively large particle sizes 3 and a rapid drying vice versa.Moreover, it is found that the distribution of the particles depositedconsists in a gradual increase tendency of from the interior of a layerto the surface thereof. This tendency advantages a rapid dissolution ofthe deposited particles in a treating solution.

The present invention is applicable to various silver halidephotographic materials such as amateur films, cinema, roentgen, printingand color photography. For example, the invention can be favorablyapplied to silver chloride emulsions for copying, silver chlorobromideemulsions and sulfur sensitized, reduction sensitized, gold sensitizedand optically sensitized silver iodobromide emulsions for high-sensitivenegatives without bad influences upon their photographic characters andwithout interactions with stabilizers, hardeners, surfactants and otheradditives to be added to these emulsions.

In addition, even if the compound sprouted from a coating surface isaccumulated in a developing solution or fixing solution, its treatingaction is not hindered.

It will be understood from the above descriptions that the first, fourthand fifth object can be accomplished in accordance with the photographicmaterial of the present invention and the second, third and fifth objectcan be accomplished also if the invention is applied to a previouslytreated light-sensitive material to thereby matted its surface.

The invention will now be illustrated by the following examples:

EXAMPLE 1 A silver chlorobromide emulsion for a lithographic film and aprotective layer consisting mainly of gelatin were previously applied toone side of a support of polyethylene terephthalate having subbinglayers on the both sides, and to the opposite side were then appliedcoating solutions for antihalation so as to give a coating thickness of6:1 microns on dry basis, which had been prepared by adding 80 ml. of anaqueous solution of 10% by weight of an antihalation dye, 10 ml. of anaqueous solution of 10% by weight of chrome alum and 3 ml. of an aqueoussolution of 4% by weight of saponin to 1 kg. of an aqueous solutioncontaining 15% by weight of gelatin, and dividing the resulting solutioninto three equal parts, to each of which potassium sulfate was added inan amount of g., 2.5 g. or 5 g. The coating so obtained was firstsolidified by a cleaned air cooled to 7 C. and then dried by passingthrough a tunnel type drying chamber where the dry bulb temperature wasgradually increased from 18 to 40 C., the drying being accomplished forabout 35 minutes. In the case of adding potassium sulfate, its finecrystals having a particle size of about 3-6 microns in diameter weredeposited on the surface uniformly to mat it.

The thus resulting films having difierent antihalation layers wereconditioned in an atmosphere of 90% RH. and 35 C. for 48 hours, allowedto stand for further 24 hours in the same atmosphere with protectivelayers piled thereon under a static pressure of 50 g./cm. and thereafterthe areas adhered were compared. At the same time, the coatings of theantihalation layer only with respect to the foregoing coating solutionswere immersed in water at 18 C. for 30 seconds, dried and the sproutingvelocities of the matting agent particles were compared while definingthe transparency of the film free of the matting agent, i.e., potassiumsulfate to 100. The results were tabulated below.

4 EXAMPLE 2 Amount of zinc Area adhered, percent Transparency altersulfate (g.) water treatment EXAMPLE 3 An antihalation layer consistingmainly of gelatin and an antihalation dye was previously applied to theone side of a support of cellulose triacetate having subbing layers onthe both sides, and to the other side were applied firstly a silveriodobromide emulsion for panchromatic high sensitivity negatives,followed by drying, and then a coating solution for protecting so as togive a coating thickness of 15:0.5 micron on dry basis, which had beenprepared by adding 15 ml. of an aqueous solution of 2% by weight ofmucochloric acid, 5 ml. of an aqueous solution of 10% by weight ofchrome alum and 2 ml. of an aqueous solution of 4% by weight of saponinto 1 kg. of an aqueous solution containing 3% by weight of gelatin anddividing the resulting solution into two equal parts, in each of whichsodium sulfate was dissolved in an amount of 0 g. or 3 g. The coatingsso obtained were solidified by a clean air cooled to 7 C. and then driedby passing through a tunnel type drying chamber where the dry bulbtemperature of the air was gradually raised from 18 to 35 C., the dryingbeing accomplished for about 30 minutes. In the case of adding sodiumsulfate, its fine crystals having a particle size of about 2-5 micron indiameter were uniformly deposited to thereby mat the layer surface.

The ratios of the areas adhered were compared in the similar manner toExample 1 with respect to the thus resulting films having the foregoingtwo different protective layers. Further, the coeflicients of staticalfriction of the protective layers to an antihalation layer were measuredand compared after conditioning the coatings in an atmosphere of 65% RH.and 23 C. for 48 hours. The quantity of electrification was measured asfollows. Two test pieces of 2.5 cm. x 20cm. were cut from the two filmsrespectively, adhered to the both sides of an adhesive tape in such amanner that the each protective layer was exposed, conditioned in anatmosphere of 40% RH. and 23 C. for 48 hours, passed through two hardrubber rollers revolving in tight contact each other and the quantitiesof electrification thereon were found by means of a Faraday cage. Theresults were tabulated below.

As antihalation layer consisting mainly of gelatin and an antihalationdye was applied previously to the one side of a support of polyethyleneterephthalate having subbing layers on the both sides, and to the otherside was applied a coating solution so as to give a coating thickness of7:1 micron on dry basis, which had been prepared by adding 20 ml. of amethanol solution of 1% by weight of a fog inhibitor, 20 ml. of anaqueous solution of 2% by weight of mucochloric acid, 10 ml. of anaqueous solution of 10% by weight of chrome alum, 3 ml. of an aqueoussolution of 4% by weight of saponin and 30 ml. of an aqueous solution of20% -by weight of hydroxypropyl starch to l kg. of a silverchlorobromide emulsion for copying containing about 7% by weight ofgelatin and dividing the resulting coating solution into two equalparts, in each of which potassium sulfate was dissolved in an amount of0 g. or 3.5 g. The drying conditions were substantially similar toExample 1. In the case of adding potassium sulfate, fine crystals havinga particle size of about 2-6 micron in diameter were deposited on thelayer surface to thereby mat it. The quantities of electrification weremeasured in the similar manner to Example 3 with respect to the twofilms so obtained to give the following "results tabulated.

Amount of Potassium Sulfate, g.: Quantity of electrification (v.) 0100-110 3.5 60- 70 It is well known that a water soluble salt is addedin the step of producing a photographic emulsion or salts areby-produced in the production of a photographic emulsion. For example,it has been proposed to carry out water washing of a photographicemulsion effectively by the use of a large amount of sodium sulfate toprecipitate the gelatin in the emulsion with the silver halide. When asilver bromide emulsion is prepared by the reaction of silver nitratewith potassium bromide, potassium nitrate remains in the emulsion. Inthe prior art, however, such salt was removed as a harmful matter. Onthe contrary, the present invention is based upon the discovery that thepresence of a non-deliquescent crystalline compound of water solublesalts rather advantages the matting action only if deposited on thesurface of a layer as fine crystals.

We claim:

1. A process for producing a photographic light sensitive materialhaving a matted surface comprising:

. (A) applying an antihalation layer consisting mainly of gelatin and anantihalation dye to one side of a support of polyethylene terephthalatehaving subbing layers on both sides;

(1B) applying a coating solution to the other side of said support so asto give a dry coating thickness of 6-8 microns prepared as follows:

(i) add ml. of a methanol solution of 1% by weight of a fog inhibitor;

(ii) add 20 ml. of an aqueous solution of 2% by weight of mucochloricacid;

(iii) add 10 ml. of an aqueous solution of 10% by weight of chrome alum;

(iv) add 3 ml. of an aqueous solution of 4% by weight of saponin;

(v) add 30 ml. of an aqueous solution of by weight of hydroxypropylstarch, to

(vi) 1 kg. of a silver chlorobromide emulsion for copying containingabout 7% by weight of gelatin;

(C) dividing the resulting coating solution into first and second equalparts;

(D) adding 3.5 grams of potassium sulfate 2-6 microns in diameter afterapplying said second coat;

(E) solidifying by air cooling; and

(F) drying.

2. A process for producing a photographic light sensitive materialhaving a matted surface comprising:

.(A) applying silver chlorobromide and a gelatinous protective layer toone side of a polyethylene terephthalate support;

(B) sequentially applying to the other side of said support a series offirst, second and third coating solutions approximately six microns indry thickness and prepared as follows:

(i) add 80 ml. of an aqueous solution of 10% by weight of antihalationdye;

(ii) add 10 ml. of an aqueous solution of 10% by weight chrome alum; and

(iii) add 3 ml. of an aqueous solution of 4% by weight of saponin, to

(iv) 1 kg. of an aqueous solution containing 15% by weight of gelatin;

(v) dividing the resultant solution into first, second and third parts;

.(vi) applying said parts as a first coating, second coating and a thirdcoating;

(vii) adding 2.5 grams potassium sulfate fine crystals having a particlesize of about 3-6 microns in diameter after applying the second coating;

(viii) adding 5 grams of potassium sulfate fine crystals having aparticle size of about 3-6 microns in diameter after applying said thirdcoat (C) solidifyingthe coatings so obtained by air cooling toapproximately 7 C.;

(D) drying by passing said material through an environment of 18-40" C.approximately 45 minutes; (E) conditioning said material in anatmosphere at 90% relative humidity and 35 C. for 48 hours; and

(F) applying approximately 50 g./cm. pressure to said coatings.

3. A process for producing a photographic light sensitive materialhaving a matted surface comprising:

.(A) applying silver chlorobromide and a gelatinous protective layer toone side of a polyethylene terephthalate support;

(B) sequentially applying to the other side of said support a series offirst and second coating solutions approximately six microns in drythickness and prepared as follows:

(i) add ml. of an aqueous solution of 10% by weight of antihalation dye;

(ii) add 10 ml. of an aqueous solution of 10% by weight chrome alum; and

(iii) add 3 ml. of an aqueous solution of 4% by weight of saponin, to

(iv) 1 kg. of an aqueous solution containing 15% by weight of gelatin;

(v) dividing the resultant solution into first and second parts;

.(vi) applying said parts as a first coating and a second coating; and

(vii) adding 5 grams zinc sulfate fine crystals having a particle sizeof about 3-6 microns in diameter after applying said second coating.

4. A process for producing a photographic light sensitive materialhaving a matted surface comprising:

(A) applying an antihalation layer consisting mainly of gelatin and anantihalation dye to one side of sup port of cellulose triacetate havingsubbing layers on both sides;

(B) applying silver iodobromide emulsion for panchromatic high sensitivenegatives to the other side;

(C) drying said support;

(D) sequentially applying to the other side of said sup port a seriesoffirst and second coatings so as to give an approximately 1 to 2 microndry coating thickness, each coating being prepared as follows:

(i) add 15 ml. of an aqueous solution of 2% by weight of mucochloricacid;

.(ii) add 5 ml. of an aqueous solution of 10% by weight of chrome alum;

(iii) add 2 ml. of an aqueous solution of 4% by weight of saponin, to

(iv) 1 kg. of an aqueous solution containing 3% by weight of gelatin;

(v) dividing the resulting solution into two equal parts and applyingone of said parts as first coating;

(vi) adding sodium sulfate crystals 2-5 microns in diameter 3 gramsuniformly to another of said parts and applying as said second coating;

(E) solidifying by air cooling at approximately 0 C.;

(F) drying at a temperature range 18-35 C.; and

.(G) conditioning said coating in an atmosphere of 7 8 approximately 65%relative humidity and 23 C. for 3,224,878 12/1965 Klimkbwski et :11. 11734 X 48 hours. 3,297,477 1/1967 Barkis et a1 117161 References CitedUNITED STATES PATENTS WILLIAM D. MARTIN, Pnmary Examlner Roche X 5 W- R-Assist nt Examiner 804,039 11/1905 Pifer 11734 1,631,421 6/1927 Lolofer117-34 1,901,441 3/1933 Frankel 96-94 96-67, 94; 11742 2,221,873 11/1940Knoefel 11734 X

